Fatty derivatives of aminoalkyl and hydroxyalkyl heterocyclic amine bases as asphalt additives



United States Patent Ofiice 3,114,649 Patented Dec. 17, 1%53 3,114,649 DERFJATEVES @F @ALKYL AND HY- DRUX ALKYL HET FRUQYQMC AltdlNlE BASES A5; ASFl-KA'LT ADDETWES Face-b Kata, l5 Bevelin Road, Providence, RI. No Drawing. Filed 3, E60, Ser. No. 26,444 7 Claims. er. ll%-273) The present invention relates to fatty derivatives of substituted heterocyclic polyamines used as additives in asphalt and bituminous compositions and additives thereror.

The present invention is particularly directed to piperazineeterocyclic asphalt compositions and piperazineheterocyclic asphalt emulsion compositions and is also directed to novel wetting and anti-stripping agents for use in such compositions.

An object of the present invention is to provide a new class of wetting and anti-stripping agents for use in bituminuous paving materials and particularly in connection with asphalts, asphalt emulsions and tars, which will assure adherence of these asphalt or tarry materials to various types of aggregates.

Another object is to provide novel asphalt and bituminous combinations which will coat and adhere to wet or dry aggregates, whether of siliceous or basic, or granite or limestone character, and regardless of their acid or basic surface qualities and which will provide a durable long lasting adhesive bond without special processing and with the use of minimum quantities of the additive antistripping or wetting agent.

A further object is to provide bituminous asphalt or tarry compositions for adherence to aggregate which will not be subject to decomposition or loss of wetting and anti-stripping properties with prolonged heating or when subject to elevated temperatures ranging from 250 to 400 F. and Which will have undirninished high Wetting and anti-stripping properties over long periods of time.

Still further objects and advantages will appear in the more detailed description set forth below, it being understood, however, that this more detailed description is given by Way of illustration and explanation only and not by way of limitation, since various changes therein may be made by those skilled in the art without departing from the scope and spirit of the present invention.

it has now been found that unusually effective wetting and anti'stripping agents which are stable over long periods of time and at elevated temperatures of 250 to 400 F. may be prepared by the reaction of aliphatic heterocyclic polyamino compounds with high molecular weight organic acids.

The preferred aliphatic heterocyclic polyarnino compounds comprise thereof as morpholinopropylamine, piperidinopropylamine, N-aminoethylpiperazine, N-hydroxyethy-lpiperazine, aminopropylpiperazine, di-(morpholinopropyl) amine and l N, N-aminopropyl piperazine Desirably, these basic polyamino compounds are reacted with two to three mols of a fatty acid having 8 to 22 carbon atoms to amidize the primary and secondary amine groups and to form fatty acid salts with the tertiary amine groups.

It has been found these fatty acid compounds of the above basic materials are highly soluble in asphalt and bituminous substances and have high heat stability and will impart unusual wetting and anti-stripping properties to same.

The important polyamines are those which have a predetermined ratio of tertiary and amide forming nitrogen atoms preferably in a straight or branch chain with there being at least one tertiary salt-forming nitrogen atom in the heterocyclic polyamino compound.

it has been found that the alkyl groups present may be methyl, ethyl, propyl, butyl or isopropyl, while the fatty acid groups may be stearic acid, palmitic acid, oleic and ricinoleic acid, tall oil fatty acids, abietic acid, soya fatty acids, tallow fatty acids, naphthenic acid and/or dimerized fatty acid compositions.

The above cyclic polyamino compounds may be derived by reacting morpholine or piperidine with acrylonitrile to form a nitrile and hydrogenating the resulting nitrile to an amine. The substituted piperazines are synthesized from diethylenetriamine and aminoethylethanolamine.

EXAMPLE 1 One mol of piperidinopropylamine and two mols of tall oil fatty acids containing approximately 45% abietic acid are charged into a one liter three neck flask equipped with a thermometer, stirrer, water trap and condenser.

The mixture is heated by a woven glass mantle to 350 F. and held at this temperature until 18 ml. (one mol) of water is collected in the trap (approximately three hours).

The resulting compound is a brownish extremely viscous substance having the following formula:

where R stands for an aliphatic long chain present in tall oil fatty acid group.

In the above formulation, the abietic acid at the temperature of 350 F. will practically monopolize the salt forming position attached to the tertiary nitrogen, whereas R forming amide group will be primarily oleic and linoleic with a negligible amount or very small proportion of abietic.

EXAMPLE 2 On mol morpholinopropylamine and one mol soya fatty acids were reacted at 350 F. in a one liter three neck flask containing m1. Xylol.

Upon the azeotropic removal of one mol of water, the Xylol was stripped from the reaction mixture and 300 grams of 50% rosin-tall oil fatty acids was added.

The resulting product was a viscous red brown oil having the following formula:

Where R stands for an alihpatic long chain present in a tall oil fatty acids group and R stands for an aliphatic long chain present in a soya fatty acid group.

In the above example, the R amide group will be ta ten up by the soya fatty acid at 350 F. Then when the tall oil fatty acids are added, the various fatty acids including abietic, oleic and linoleic acids will make up the salt forming R group.

The tall oil fatty acid used has a 50% abietic and/ or rosin content. However, the strength of rosin or abietic acid may vary from 33 to 60% in the tall oil fatty acids.

EXAMPLE 3 One mol of N-aminoethylpiperazine was reacted with three mols of mixed vegetable fatty acids derived from castor oil at 350 F. for for four hours until 36 ml. of water was collected in the separator.

The final product was a brown black waxy material soluble in alcohol, benzene and kerosene and had the formula:

where R R and R are an aliphatic long chain present in castor oil fatty acid groups.

These castor oil fatty acids are derived from the still bottoms resulting from castor oil distillation procedures. R COOH is a salt forming group attached to the tertiary nitrogen.

EXAMPLE 4 One mol of N-hydroxyethylpiperazine and three mols of tall oil fatty acids containing 33% rosin acids was reacted at 350 -375 F. until two mols of water was collected in the water trap.

The resulting compound was a viscous reddish-brown liquid having the following formula:

GHQ-CH2 R ON NCH2CH2OOCR2 CH -Cfiiabietate where R and R are groups containing an aliphatic long chain present in tall oil fatty acid groups.

In this reaction, the R and R of the oleic and linoleic acids first combine in mixture with the terminal reactive group and with the abietic acid finally combining with the tertiary amine to form a salt. The R acid grouping combines with the secondary nitrogen to form an amide. The R acid group forms an ester with the hydroxy groups. R and R related to the same oleic-linoleic compositions.

The compounds of Examples 3 and 4 include an additive consisting of a high molecular weight fatty acid compound having 14 to 22 carbon atoms which fatty 4 acid has been condensed with a piperazine ring compound and having at least two aliphatic side chains attached to at least one nitrogen of the ring, one side chain including a fatty acid residue having 14 to 22 carbon atoms another side chain polymethylene linkage having 2 or 3 carbon atoms and terminating in an amino group carrying a fatty acid residue having 14 to 22 carbon atoms.

Specifically they have the formula Or more specifically the formulae OH2OII2 III (I? NCHzCH2CH2-N-OR CH1CH: Abietate where R stands for an aliphatic long chain present in tall oil fatty acid group.

where R R and R are aliphatic long chains present in fatty acid groups containing 12 to 22 carbon atoms.

CID-CH1 Abtetate Where R and R are respectively groups containing aliphatic long chains present in tall oil fatty acid groups.

The above derivatives were evaluated for their wetting and anti-stripping properties by incorporating 1% in MC-3 asphalt by the method as outlined below.

Ninety-nine grams samples of MC3 liquid asphalt was thoroughly blended with one gram of asphalt additive as prepared in Examples 1 to 4 in a half pint friction-top can. The containers were placed in an oven maintained at a temperature of 325 F. for 72 hours, at the end of which period of time, the samples were removed and cooled to 175 F.

At the same time 100' grams of MC-3 asphalt without additive was heated for the same period under the same conditions to give a blank run.

Wet Coating Test Stripping Test The coated aggregate from the Wet Coating Test Was formed into a compact mass one inch thick and cured for one hour at 140 F.

The cured mixes were then immersed in distilled water at room temperature and allowed to remain for 18 hours. At least 95% of the aggregate surfaces was coated at the end of the immersion period.

The blank of MC-3 asphalt failed the test with Zero coating.

The following are the results of 72 hour heat stability test at 325 F.

TABLE I.WET COATING TEST [Percent coated] Massa- New Ohio Virginia M 0-3 Asphalt: plus Additive chusetts York Silica Lime- Rhyolitc Granite stone Example 1 96 95 100 Example 2. 100 100 Example 3. 100 100 100 95 Example 4.." 100 100 100 100 TABLE II.-EIGHTEEN I-IOUR WATER IMMERSION TEST [Percent coated aggregate] Massa- New Ohio Virginia M C-3 Asphalt plus Additive chusetts York Silica Limo- Rhyolitc Granite stone Example 1 9O 95 95 90 Example 2 90 100 90 90 Example 3 95 100 90 90 Example 4 95 95 90 100 The additive compounds are added in amounts ranging from A to 30% of the weight of the asphalt or bituminous material or tar. Preferably the range is /2 to 1%% by weight of the asphalt.

Usually, the additive is included in asphalt compositions such as medium cure, cutback with 30% kerosene,

or rapid cure cutback 30% diesel oil or gasoline, or slow cure asphalt. These are generally asphalts cutback with 20 to 50% of solvent.

The preferred fatty acids are those having from 8 to 36 carbon atoms and preferably those having 14 to 22 carbon atoms.

The tall oil, oleic and linoleic acids have 18 carbon atoms and abietie acid has 20 carbon atoms, and these are preferred.

The piperazines of Examples 3 and 4 are preferred and are most effective and piperazine is generally better and more effective than the morpholines.

Having now particularly described and ascertained the nature of the invention, and in what manner the same is to be performed, What is claimed is:

1. The method of preparing a high temperature stabilized coating composition and enhancing the bonding, wetting and anti-stripping properties of asphalt, tar and bituminous coating compositions for basic aggregates, including limestone and dolomite, which will be stable at temperatures of above 300 F. and between 350 and 450 R, which comprises adding to the coating compositions /2 to 1 /2 by weight of the composition an additive consisting of a high molecular weight piperazine compound having at least two aliphatic side chains attached to at least one nitrogen of the ring, one side chain including a fatty acid residue having 14 to 22 carbon atoms and the other side chain containing a polymethylene linkage having 2 to 3 carbon atoms and terminating in an amino group carrying a fatty :acid residue having 14 to 22 carbon atoms.

2. The method of preparing -a high temperature stabilized coating composition and enhancing the bonding, wetting and anti-stripping properties of asphalt, tar and bituminous coating compositions for basic aggregates, including limestone and dolomite, which will be stable at temperatures of above 300 G. and between 350 F. and 450 *F., which comprises adding to the coating compositions /2 to 1 /2 by weight of the composition an additive consisting of a high molecular weight compound having the general formula containing 14 to 22 carbon atoms and n represents a numeral ranging from 2 and 3 carbon atoms.

6 3. The method of claim 1 in which the additive is /CHCH 1ft $1) N\ N-CH2CH2CI'I2NC R OIL-CH2 Abletate where R stands for an aliphatic long chain present in tall oil fatty acid group.

4. The method of claim 1 in which the additive is CHz-OH2 I R1OON NCH2CH2NOCR2 GHQ-CH: H o

o 0 s where R R and R are aliphatic long chains present in fatty acid groups containing 12 to 22 carbon atoms.

5. The method of claim 1 in which the additive is CHz-CHZ Abietate Where R and R are respectively amide and ester groups containing aliphatic long chains present in tall oil fatty acid groups.

6. The method of claim 1 in Which the additive is 2,468,163 Blair et al. Apr. 26, 1949 2,658,895 Ballard et a1 Nov. 10, 1953 2,737,509 Jelling Mar. 6, 1956 2,766,132 Blair et al. Oct. 9, 1956 

1. THE METHOD OF PREPARING A HIGH TEMPERATURE STABILIZED COATING COMPOSITION AND ENHANCING THE BONDING, WETTING AND ANTI-STRIPPING PROPERTIES OF ASPHALT, TAR AND BITUMINOUS COATING COMPOSITIONS FOR BASIC AGGREGATES, INCLUDING LIMESTONE AND DOLOMITE, WHICH WILL BE STABLE AT TEMPERATURES OF ABOVE 300*F. AND BETWEEN 350*F. AND 450*F., WHICH COMPRISES ADDING TO THE COATING COMPOSITIONS 1/2 TO 1 1/2% BY WEIGHT OF THE COMPOSITION OF ADDITIVE CONSISTING OF A HIGH MOLECULAR WEIGHT PIPERAZINE COMPOUND HAVING AT LEAST TWO ALIPHATIC SIDE CHAINS ATTACHED TO AT LEAST ONE NITROGEN OF THE RING, ONE SIDE CHAIN INCLUDING A FATTY ACID RESIDUE HAVING 14 TO 22 CARBON ATOMS AND THE OTHER SIDE CHAIN CONTAINING A POLYMETHYLENE LINKAGE HAVING 2 TO 3 CARBON ATOMS AND TERMINATING IN AN AMINO GROUP CARRYING A FATTY ACID RESIDUE HAVING 14 TO 22 CARBON ATOMS. 